EP0775682B1 - Verfahren zur Herstellung von Camphen durch Umlagerung von alpha-Pinen - Google Patents

Verfahren zur Herstellung von Camphen durch Umlagerung von alpha-Pinen Download PDF

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Publication number
EP0775682B1
EP0775682B1 EP96118575A EP96118575A EP0775682B1 EP 0775682 B1 EP0775682 B1 EP 0775682B1 EP 96118575 A EP96118575 A EP 96118575A EP 96118575 A EP96118575 A EP 96118575A EP 0775682 B1 EP0775682 B1 EP 0775682B1
Authority
EP
European Patent Office
Prior art keywords
pinene
reaction
camphene
reaction mixture
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96118575A
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German (de)
English (en)
French (fr)
Other versions
EP0775682A1 (de
Inventor
Manfred Dr. Gscheidmeier
Harald Dr. Häberlein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant GmbH
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Filing date
Publication date
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Publication of EP0775682A1 publication Critical patent/EP0775682A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/29—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of carbon atoms in a ring while maintaining the number of rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Definitions

  • the present invention relates to an improved method of manufacture of camphene with a strong compared to previously known methods reduced content of isomeric tricyclic acid, at the same time as the formation of high-boiling terpene polymers is largely avoided.
  • camphene by isomerization of ⁇ -pinene using heterogeneous Catalysis has long been known (L.G. Gurvich, J. Russ. Phys,. Chem. Soc., 47, 827/1915).
  • Various types of catalysts have been proposed for this purpose acidic titanium dioxide hydrate has proven particularly effective (summary: Ullmann's Encyclopedia of Technical Chemistry, 3rd Edition, Volume 17, 1966).
  • the reaction produces camphene in addition to the main product several by-products such as tricyclic, dipentene, isomeric p-mentadienes and Polymers.
  • Cyclofenchen ⁇ -Fenchen, Bornylen, ⁇ -3-Caren, p-Cymol, p-Menthen-3 and diterpenes.
  • Camphen plays an important role as an intermediate, e.g. B. for production of terpene nests (inexpensive and often nature-identical fragrances, such as Isobornyl acetate, or monomers for coating resins), terpene oxygen compounds (Isoborneol, camphor), terpene ethers or alkylation products (e.g. Phenols). It is often important that the tricyclic content in Camphene is below 10% if possible.
  • terpene nests inexpensive and often nature-identical fragrances, such as Isobornyl acetate, or monomers for coating resins
  • terpene oxygen compounds Isoborneol, camphor
  • terpene ethers or alkylation products e.g. Phenols
  • the isomerization reaction is highly exothermic, so heat must be removed become. This can e.g. by direct cooling or pumping over a Cooling unit take place to keep the temperature below the boiling range hold. This has the advantage of the low catalyst requirement (0.05-0.1% by weight) and slightly higher camphene yield while avoiding the Formation of high-boiling by-products. However, the reaction then needs 10 - 15 times the time compared to carrying out a reaction on Product boiling point. In this case the heat of reaction is by evaporation of ⁇ -pinene or of reaction products with subsequent condensation dissipated, i.e. the reaction mixture is allowed to reflux (C.A. Vol. 89/1978, 197 725 g; EP-A-0 539 990).
  • This polymerization reaction can now be avoided by reaching a certain ⁇ -pinene content lowers the reaction temperature and at this temperature brings the reaction to an end. You can quickly reach it Reaction by refluxing, but avoided by lowering the Temperature in the final phase the formation of high-boiling polymers Products as far as possible.
  • the invention thus relates to a method for producing camphene by rearrangement of ⁇ -pinene in the presence of a titanium oxide hydrate catalyst in the heat, with ⁇ -pinene first being heated under reflux until the ⁇ -pinene content in the reaction mixture is at least 3, preferably 5 Wt .-%, and then the rearrangement in a post-reaction a temperature below 160 ° C, preferably at 150-155 ° C.
  • the process can be carried out in detail in such a way that the ⁇ -pinene and the catalyst is placed in a stirred tank and covered with nitrogen, preferably with a heating rate of 0.5 to 10, preferably 2 to 4 ° C / min is heated to reflux temperature.
  • the Heat of reaction is removed by evaporative cooling.
  • the reflux temperature i.e. the boiling point of ⁇ -pinene or that which arises in the course of the rearrangement Reaction mixture depends on the purity of the ⁇ -pinene. Generally lies the reflux temperature at about 155 to 165 ° C.
  • the response time is 0.3 to 3.5, preferably 0.7 to 1.5 h depending on the catalyst concentration and Heating rate.
  • the catalyst is a conventional titanium oxide hydrate, preferably a titanium oxide hydrate, which is obtained as follows: A sulfuric acid TiO 2 paste is mixed with NaOH solution, then washed and stirred with acetic acid, suction filtered and then dried at 50 to 100, preferably at 60 to 80 ° C. in vacuo.
  • the amount of catalyst to be used is 0.1 to 2.0, preferably 0.3 up to 0.5% by weight, based on pure ⁇ -pinene.
  • the reaction mixture When the reflux temperature is reached, the reaction mixture is as long kept at this temperature until the content of ⁇ -pinene in the reaction mixture to approximately 3% by weight, preferably to approximately 5% by weight.
  • the ⁇ -pinene content can be reduced in the course of the rearrangement reaction easily by suitable analytical methods, for example by Gas chromatography, track. If these residual amounts of ⁇ -pinene in Reaction mixture are reached, the internal temperature of the Reaction mixture lowered and the conversion of the remaining ⁇ -pinene completed in a post-reaction at lower temperatures.
  • the Temperature in this post-reaction depends on the boiling point of the Reaction mixture. It makes sense to change the temperature during the after-reaction about 10 ° C below the boiling point of the reaction mixture.
  • the duration of the post-reaction depends of the desired residual content of ⁇ -pinene. If the one you want Residual amount, for example 0.1% by weight of ⁇ -pinene, is reached Cooled reaction mixture, filtered off the catalyst and the camphene separated from the by-products by distillation.
  • one is used less active titanium oxide hydrate catalyst or a smaller amount of one more active catalyst of this type.
  • the main reaction then requires something more time, but here the reaction temperature drops towards the end of the ⁇ -pinene isomerization by itself below the boiling temperature, so that one for the After-reaction can do without active cooling.
  • Tricycles the proportion of tricycles depending on the reaction temperature. At a reaction temperature of 155 ° C, for example, 13.6 % By weight of tricycles in the reaction mixture or 17.1% by weight in that of p-mentadiene liberated faction. It has now been found that this Set the equilibrium value even when using a product mixture high tricyclic content the isomerization conditions as with ⁇ -pinene submits. The equilibrium value sets in much faster here than in Isomerization of a mixture with a correspondingly lower tricyclic content.
  • the tricyclic-rich distillation section alone Subject to isomerization conditions as with ⁇ -pinene. It is advantageous that no p-mentadienes and therefore no high-boiling By-products occur.
  • the first section from the raw camphene distillation gives a main camphene fraction, which now contains significantly fewer tricycles on average, each according to the tricyclic content and amount of the first section to well below 10%.
  • the method according to the invention thus enables the proportion of polymer Lower and by-products in the conversion of ⁇ -pinene to camphene thereby increasing the proportion of camphene. It is also possible through the Separation of a first tricyclene-rich fraction in the distillative Processing of the reaction mixture and recycling of this enriched Fraction in the isomerization reaction to the proportion of tricyclene in the camphene reduce.
  • Example 2 Analogously to Example 1, 3000 kg of ⁇ -pinene and 350 kg of tricyclic lead were (with 49% tricyclic) with 7.5 kg weakly acidic titanium dioxide hydrate for the reaction brought. The reaction temperature rose to 161.2 ° C and then started to increase slightly fall. After about 120 minutes, the reaction was stopped by cooling. The reaction mixture contained only 0.2% by weight of high-boiling polymer components; the weight ratio of tricycles, camphene and p-mentadiene was 1: 4.5: 1.3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
EP96118575A 1995-11-27 1996-11-20 Verfahren zur Herstellung von Camphen durch Umlagerung von alpha-Pinen Expired - Lifetime EP0775682B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19544086A DE19544086A1 (de) 1995-11-27 1995-11-27 Verfahren zur Herstellung von Camphen durch Umlagerung von alpha-Pinen
DE19544086 1995-11-27

Publications (2)

Publication Number Publication Date
EP0775682A1 EP0775682A1 (de) 1997-05-28
EP0775682B1 true EP0775682B1 (de) 1999-03-03

Family

ID=7778475

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96118575A Expired - Lifetime EP0775682B1 (de) 1995-11-27 1996-11-20 Verfahren zur Herstellung von Camphen durch Umlagerung von alpha-Pinen

Country Status (8)

Country Link
US (1) US5826202A (no)
EP (1) EP0775682B1 (no)
JP (1) JP3897385B2 (no)
AT (1) ATE177076T1 (no)
CA (1) CA2191300C (no)
DE (2) DE19544086A1 (no)
ES (1) ES2131374T3 (no)
NO (1) NO306775B1 (no)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105080532A (zh) * 2015-09-07 2015-11-25 广西梧州通轩林产化学有限公司 莰烯生产用催化剂的制备方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8518130B2 (en) * 2010-03-10 2013-08-27 Shell Oil Company Relating to fuels
CN103415600B (zh) 2011-03-10 2015-11-25 国际壳牌研究有限公司 关于汽油燃料制剂改进
CN104496741A (zh) * 2014-12-16 2015-04-08 上海华谊（集团）公司 蒎烯异构化生成莰烯和三环烯的方法
CN105218292A (zh) * 2015-09-07 2016-01-06 广西梧州通轩林产化学有限公司 莰烯的制备方法
CN105056930A (zh) * 2015-09-07 2015-11-18 广西梧州通轩林产化学有限公司 莰烯生产用催化剂的制备方法
CN107459445B (zh) * 2017-07-27 2021-01-15 福建南平青松化工有限公司 樟脑脚油回收利用的方法
CN110698316A (zh) * 2019-11-26 2020-01-17 天门市德远化工科技有限公司 一种1,1,3,5-四甲基-3-异丙基二氢化茚的合成方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2551795A (en) * 1949-06-23 1951-05-08 Du Pont Process for making camphene
DE4136041A1 (de) 1991-11-01 1993-05-06 Hoechst Ag, 6230 Frankfurt, De Verfahren zur herstellung von camphen durch umlagerung von (alpha)-pinen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105080532A (zh) * 2015-09-07 2015-11-25 广西梧州通轩林产化学有限公司 莰烯生产用催化剂的制备方法

Also Published As

Publication number Publication date
DE19544086A1 (de) 1997-05-28
NO965022D0 (no) 1996-11-26
CA2191300A1 (en) 1997-05-28
JP3897385B2 (ja) 2007-03-22
NO965022L (no) 1997-05-28
EP0775682A1 (de) 1997-05-28
JPH09169670A (ja) 1997-06-30
ATE177076T1 (de) 1999-03-15
DE59601376D1 (de) 1999-04-08
NO306775B1 (no) 1999-12-20
ES2131374T3 (es) 1999-07-16
CA2191300C (en) 2007-04-03
US5826202A (en) 1998-10-20

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